Producing dischargeable dyeings on acetate silk



Patented Mar. 22, 1932 UNITED STATES PATENT OFFICE GUSTAV REDDELIEH, 01" LEIPZIG, AND GEORG MATZDORF AND ALFRED PETERS, OI DESSAU IN AN'HALT, GERMANY, ASSIGNOBS TO GENERAL ANILINE WORKS, INC., 01? NEW YORK, N. Y., A CORPORATION OF DELAWARE PRODUCING DISCHARGEAIBLE DYEINGS ON ACETATE SILK Ho Drawing. Application filed Kay 15, 1930,5eria1 No. 452,808, and in Germany May 38, 1929.

Our present invention relates to a new process of producing dischar eable dyemgs on acetate silk; one of its jects are t e threads of acetate silk or the fabrics made of 5 acetate silk dyed according to our new process.

We have found that dark green, navy blue and black shades which can be discharged white, are obtainable on acetate silk by dyeing it with a dye of the general formula:

wherein R represents a phenyl radical, substituted or not by halogen, alkyl, alkoxyl or several of these groups; R a phenyl radical or naphthyl radical, substituted or not by halogen or alkyl, and X an aliphatic radical, such as CH C 11 CH CH OH, diazotizing these dyes on the fiber and developing them with 2 hydroxynaphthalene 3 carboxylic acid. The d es necessary to this end can be obtained in own manner by coupling the corresponding nitroaminodiazo or acylamino diazo compounds with the tertiary amines and subsequently reducing the nitro-group or splitting off the acyl radical.

Thus the monoazo tertiary amino compounds in question may be made according to 30 or in analogy with the process disclosed in the Journal of the Chemical Society, vol. 45, page 107.

The following examples illustrate the invention:

Example 1.1 kilo of acetate silk is put into a bath containing 30 liters of water,

20 ams of the dye of the following constitutionz 4o OCH: CH

nm N =NQN/ \CH: 0H; 0

90 grams of soap.

The dye mentioned above is rather difiicultly soluble in alcohol. Recrystallized from ethyl alcohol it forms small red-brown crystals or a red powder when pulverized. It melts at 177 C.

The dye is first made into a paste with some Water, if necessary, while adding somesoap or any other emulsifying agent, and then entered into the dyeing bath mixed with soap. In the dyeing bath the material is treated for about three quarters of an hour starting at about 40 C. and then gradually raisin the temperature to 70 G. Then the materia is rinsed and diazotized durin 20 to 30 minutes in a fresh cold bath consisting of 30 liters of water, 60 grams of sodium nitrite, and 150 grams of hydrochloric acid of 20 B. After diazotizing the material is well rinsed and developed in a bath containing 60 g. of 2-hydroxynaphthalene-S-carboxylic acid for 30 liters of water. Next the requisite quantity of hydroxynaphthalenecarboxylic acid is dissolved b boiling while adding twice the quantity 0 sodium acetate and the solution is added to the developing bath. In thisdeveloping bath the material is treated for about half an hour, entering it in the lukewarm bath and raising the temperature of the latter slowly to 60 C.

A deep dark-green is obtained which can be discharged by the usual reduction discharges, for instance, pure white by the mono zinc salt of the formaldehyde sulfoxylic acid.

Emample 2.Dyeing is carried out according to the method indicated in Example 1, by substituting 40 g. of the dye of the following constitution i for the dye used in said example.

This dye is considerably soluble in ethyl alcohol; recrystallized therefrom it forms bronze-colored crystals which may be pulverized to form a yellow-brown powder. It melts at about 107 C. The shade obtained is a deep marine blue having a very good dischargeability.

Example 3.-For dyeing 1 kg. of acetate silk, the dyeing bath containing about 30 liters of water, is prepared with 12 grams of the dye of the following constitution:

This dye is easily soluble in alcohol from a hot concentrated solution. It crystallizes in form of small red-brown crystals which pulverized form a red powder. It melts at 171 to 172 C. The dye is dissolved by pouring over it the same or 1 its weight of hydrochloric acid of 20 B. Then the solution obtained is added to the dyeing bath. The material is entered in the lukewarm bath; the temperature is then raised to to C. within 4 hour. For better exhausting the bath another 150 to 200 grams of sodium acetate are subsequently added. After about hour the material is rinsed and diazotized and developed in the manner indicated in Example 1.

A black shade with a bluish hue is obtained 'ving good white effects with the usual rediiction discharges.

Ewample .4.--The operation is the same as in Example 1, with the difference only that the dye indicated therein is substituted by that of the following constitution:

For producing a black shade on 1 kg. of ace-r charged white with the mono zinc salt of formaldehyde-sulfoxylic acid.

What we claim is:

1. The process of producing dischargeable dyeings on acetate silk, which comprises dyeing it with a dye of the general formula:

wherein R represents a phenyl radical substituted or not by halogen, alkyl or alkoxyl, R a phenyl or naphth 1 radical substituted or not by halogen or a l, and X stands for methyl, ethyl or hydroxyethyl, diazotizing the d e on the fiber and developing it with 2-hy royxnaphthalene-ii-carbox lic acid.

2. The process of roducing 'schargeable dyeings on acetate si k, which comprises dyeing it with a dye of the general formula:

wherein R relpresents a phenyl radical substitutedor not y halogen, alkyl or alkoxyl, R a phenyl or naphth l radical substituted or not by halogen or a kyl, diazotizing the dye on the fiber and developing it with 2-hydroxynaphthalene-3-carboxylic acid.

3. The process of producing dischargeable dyeings on acetate silk, which comprises dyeing it with a dye of the general formula:

wherein R respresents a phenyl or naphthyl radical substituted or not by halogen or alkyl, diazotizing the dye on the fiber and developing it with 2-hydroxynaphthalene-3-carboxylic acid.

4. The process of producing dischargeable dyeings on acetate silk, which comprises dyeing it with a dye of the general formula:

Ols OH.

diazotizing the dye on the fiber and developing it with 2-hydroxynaphthalene-3-carboxylic acid.

5. Artificial filaments consisting of acetate silk dyed in dark green, navy blue to black shades, these dyeings being dischargeable with the mono zinc salt of the formaldehyde sulfdxylic acid, said shade being efl'ected by a dye of the general formula:

wherein R represents a phenyl radical substituted or not by halogen, alkyl or alkoxyl, R a phenyl or naphthyl radical substituted or not by halogen or alkyl, and X stands for methyl, ethiydl or hydroxyethyl.

6. Artificial aments consisting of acetate silk dyed in black shades, this dyeing being dischargeable with the mono zinc salt of the formaldehyde sulfoxylie acid, said shade being effected by a dye of the general for- CERTIFICATE OF CORRECTION.

Patent No. 1,850,155.

GUSTAV REDDELIEN ET AL.

March 22, 1932.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Page 2, claims 3 and 4,

in the formulas, for the symbols "CL" and C1 respectively, read Cl; and that the said Letters Patent should be read with these corrections therein that the same may confonn to the record of the case in the Patent Office.

Signed and sealed this 5th day of July, A. D. 1932.

(Seal) M. J. Moore,

formaldehyde sulfoxylie acid, said shade being effected by a dye of the general for- CERTIFICATE OF CORRECTION.

Patent No. 1,850,155.

GUSTAV REDDELIEN ET AL.

March 22, 1932.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Page 2, claims 3 and 4,

in the formulas, for the symbols "CL" and C1 respectively, read Cl; and that the said Letters Patent should be read with these corrections therein that the same may confonn to the record of the case in the Patent Office.

Signed and sealed this 5th day of July, A. D. 1932.

(Seal) M. J. Moore, 

